CN102165024B - Pigment dispersion and aqueous ink for inkjet recording - Google Patents

Pigment dispersion and aqueous ink for inkjet recording Download PDF

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Publication number
CN102165024B
CN102165024B CN200980138266XA CN200980138266A CN102165024B CN 102165024 B CN102165024 B CN 102165024B CN 200980138266X A CN200980138266X A CN 200980138266XA CN 200980138266 A CN200980138266 A CN 200980138266A CN 102165024 B CN102165024 B CN 102165024B
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reaction
ink
water
pigment
urethane
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CN102165024A (en
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丝谷一男
木下宏司
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
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    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
    • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
    • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
    • B41J2/01—Ink jet
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8048—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/34
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • C09B67/0066—Aqueous dispersions of pigments containing only dispersing agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • C09B67/0066—Aqueous dispersions of pigments containing only dispersing agents
    • C09B67/0067—Aqueous dispersions of phthalocyanine pigments containing only dispersing agents
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/0084—Dispersions of dyes
    • C09B67/0085—Non common dispersing agents
    • C09B67/009—Non common dispersing agents polymeric dispersing agent
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
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Abstract

Disclosed is a pigment dispersion containing water, an aqueous polymer and a pigment as essential components, wherein the aqueous polymer is a carboxy group-containing polyurethane which is obtained by reacting a diol compound, a diisocyanate compound and a reaction product, which is mainly composed of a compound represented by general formula (1) and obtained by reacting a diol compound having one or two carboxy groups in each molecule and a diisocyanate compound and has a reaction index as calculated by (formula 1) of 0.95-1.10. Also disclosed is an aqueous ink for inkjet recording. Reaction index = (reaction rate of isocyanate group) (mole number of diisocyanate compound (B)/mole number of diol compound (A)) (formula 1).

Description

Dispersible pigment dispersion and water-based ink for use in ink-jet recording
Technical field
The present invention relates to use pigment as the water-based ink for use in ink-jet recording of look material.
Background technology
All the time, as water-based ink for use in ink-jet recording, use the dye ink of dyestuff with the material of showing signs of anger.Dye ink has the various advantages of the difficult print gloss excellence of stopping up and obtaining of nozzle of excellent storage stability, ink-jet printer.But it is pointed out to have by the bad print that causes of weathering resistance and can not be preserved for a long time, water tolerance, these shortcomings of being brought by dyestuff of photostabilization difference.In recent years, people are developing the water-based ink for use in ink-jet recording (being designated hereinafter simply as water-based paint printing ink) of the pigment that uses weathering resistance, water tolerance, photostabilization excellence.
Water-based paint printing ink normally is dispersed in pigment particles in the aqueous solvent such as water and the dispersible pigment dispersion that forms, and the record back forms the ink film that contains pigment particles at recording medium.The image quality of the record thing that is formed by water-based paint printing ink depends on color development and the gloss of pigment particles in this ink film itself to a great extent, use resembles the such face that is recorded of bright paper when being processed to the recording medium of level and smooth shape, exist the diffuse-reflectance of the light that causes owing to pigment particles in the ink film, the problem that the color emissivity of recording section and glossiness can suffer damage.Also exist the anchorage deficiency to recording medium in addition, the image of formation lacks the problem of erasibility.
In addition, ink jet printing is different with common printing, discharges ink droplet and prints from printhead.Piezoelectric type and hot ink jet type are arranged in this discharge mode, hot ink jet type particularly, owing to make the printing ink boiling in the nozzle that ink droplet is dispersed with the well heater that is arranged at the heating resistive element in the printhead, therefore the variation of the dramatic temperature of nozzle interior makes heater section so-called coking phenomenon (コ ゲ one シ ヨ Application) occur, the problem that liquid can not be discharged (not discharging) can occur when printing for a long time.Therefore, also require employed printing ink to have the stability of discharge.
At present, in order to improve anchorage and the gloss to recording medium, studying the aqueous pigment ink that contains resinous principle, as the printing ink that satisfies this rerum natura to a certain extent, known have a water-based ink for use in ink-jet recording that has added aqueous polyurethane.Specifically, known have contain with as tensio-active agent and the ink-jet of the urethane that known acetylenediol type hydrophobicity glycol and the glycol that contains carboxyl form as raw material with record liquid (for example referring to patent documentation 1), contain urethane-modified vibrin composition for ink jet recording (for example referring to patent documentation 2), contain the composition for ink jet recording (for example referring to patent documentation 3) from pigment dispersion and polyurethane dispersions.
But, for record liquid, exist especially at the bright paper of use during as recording medium bad problems such as the glossiness of print and anti-brush for the ink-jet of record in the patent documentation 1.In addition, the rub resistance of the discharge poor stability of the composition for ink jet recording of putting down in writing in the patent documentation 2, the print that obtains is poor, and the composition for ink jet recording of record exists the problem of discharging poor stability in the patent documentation 3.
Patent documentation 1: Japanese kokai publication hei 06-279718 communique
Patent documentation 2: TOHKEMY 2004-300393 communique
Patent documentation 3: Japanese Unexamined Patent Application Publication 2005-515289 communique
Summary of the invention
Invent problem to be solved
Also ink droplet can be stably discharged even problem to be solved by this invention provides when printing for a long time in the ink-jet printer of hot ink jet type, and weathering resistance, the particularly water-based ink for use in ink-jet recording of the printed images of erasibility excellence can be obtained.
The scheme of dealing with problems
Inventor's discovery can address the above problem by using the urethane that contains carboxyl that designs according to the mode that imports carboxyl in the macromolecular chain of urethane equably.
Without any restriction, carboxyl all is to import in the polyurethane chain at random to the urethane that contains carboxyl in the past basically on carboxyl imports.
Put down in writing the block type oligourethane in the patent documentation 1, but its objective is the control oligomeric segment, do not limited the position of carboxyl.In addition, put down in writing the synthetic aqueous polyurethane dispersion via comprising the adducts that contains acidic group two pure and mild diisocyanate cpds that contains carboxylic diol in the patent documentation 3, but do not had any record for the synthetic method of adducts.
The inventor finds out that the carboxyl that imports like this at random is very influential to discharge property.
Under the situation of carrying out random polymerization, the carboxyl import volume in a plurality of molecular chains that generate during polymerization is inhomogeneous.If particularly want the urethane control that obtains in low-molecular-weight polymerization design, then the carboxyl import volume itself on each molecular chain can reduce in theory, and therefore generation does not import the molecular chain of carboxyl sometimes.That is, even predict that in advance thereby the water-based degree determines the addition of starting monomer, because the part molecular chain of the urethane that obtains is non-water-soluble, partly reduced solvability.In addition, the part generation crosslinking reaction of isocyanic ester and carboxyl has generated unwanted gel component during polymerization in water, makes that the molecular weight of molecular weight ratio imagination is big, because crosslinked carboxyl can not play the effect that group is stablized in water-dispersion, water-soluble reduction with respect to addition.The inventor has also found these phenomenons and has found because these phenomenons are discharged stability and printing adaptability and descended significantly.
Namely, the invention provides a kind of dispersible pigment dispersion, it is with water, waterborne polymeric and pigment are as the dispersible pigment dispersion of essential composition, above-mentioned waterborne polymeric is: the compound of general formula (1) expression of reacting formation with the diol compound (A) that has 1 or 2 carboxyl in 1 molecule and diisocyanate cpd (B) is as principal constituent and resultant of reaction and the diol compound (C) of index of Response in 0.95～1.10 scope of calculating by (formula 1), and perhaps above-mentioned resultant of reaction and diol compound (C) and diisocyanate cpd (D) react the formed urethane that contains carboxyl.
(changing 1)
Figure BPA00001332752000031
(in the general formula (1), R 1And R 3The structure of the part of removing the isocyanide acyl group of expression diisocyanate cpd (B), R 1And R 3Can be identical, also can be different, R 2Represent to have in above-mentioned 1 molecule structure of the part of removing hydroxyl of the diol compound (A) of 1 or 2 carboxyl.)
Index of Response=(reactivity of isocyanide acyl group) * (mole number of the mole number/diol compound (A) of diisocyanate cpd (B))
(formula 1)
In addition, the present invention also provides the water-based ink for use in ink-jet recording of the dispersible pigment dispersion formation of using above-mentioned record.
In addition, the present invention also provides a kind of manufacture method of waterborne polymeric, it is at Yi Shui, waterborne polymeric and pigment are as the manufacture method of the waterborne polymeric that uses in must the dispersible pigment dispersion of composition, the diol compound (A) and the diisocyanate cpd (B) that have 1 or 2 carboxyl in 1 molecule are reacted, be in moment termination reaction in 0.95～1.10 scope at the index of Response of calculating by (formula 1), make with the compound of general formula (1) the expression resultant of reaction as principal constituent, then, make above-mentioned resultant of reaction and diol compound (C), above-mentioned resultant of reaction and diol compound (C) and diisocyanate cpd (D) are reacted.
(changing 2)
Figure BPA00001332752000041
(in the general formula (1), R 1And R 3The structure of the part of removing the isocyanide acyl group of expression diisocyanate cpd (B), R 1And R 3Can be identical, also can be different, R 2Represent to have in above-mentioned 1 molecule structure of the part of removing hydroxyl of the diol compound (A) of 1 or 2 carboxyl.)
Index of Response=(reactivity of isocyanide acyl group) * (mole number of the mole number/diol compound (A) of diisocyanate cpd (B))
(formula 1)
The invention effect
According to the present invention, even can provide when in the ink-jet printer of hot ink jet type, printing for a long time and also can stably discharge ink droplet, the image that does not have the irregular and ink penetration of lines can be formed, and weathering resistance, the particularly water-based ink for use in ink-jet recording of the printed images of erasibility excellence can be obtained.
If particularly the quality molecular-weight average of the above-mentioned urethane that contains carboxyl is 10,000～50, in 000 the scope, then the discharge of hot ink jet type is excellent especially.If the above-mentioned acid number that contains the urethane of carboxyl is 20～70mgKOH/g, then discharge excellent in stability.
The above-mentioned diol compound (A) that uses is if dimethylol propionic acid or dimethylolpropionic acid, and then carboxyl can import by addition substantially, is preferred therefore.
Embodiment
(dispersible pigment dispersion waterborne polymeric (urethane that contains carboxyl))
The waterborne polymeric that uses among the present invention is: the compound of general formula (1) expression of reacting formation with the diol compound (A) that has 1 or 2 carboxyl in 1 molecule and diisocyanate cpd (B) is as principal constituent and resultant of reaction and the diol compound (C) of index of Response in 0.95～1.10 scope of calculating by (formula 1), and perhaps above-mentioned resultant of reaction and diol compound (C) and diisocyanate cpd (D) react the formed urethane that contains carboxyl.
(changing 3)
Figure BPA00001332752000051
Index of Response=(reactivity of isocyanide acyl group) * (mole number of the mole number/diol compound (A) of diisocyanate cpd (B))
(formula 1)
In the general formula (1), R 1And R 3The structure of representing the part of removing the isocyanide acyl group of diisocyanate cpd described later (B), R 1And R 3Can be identical, also can be different, R 2The structure of the part of removing hydroxyl that has the diol compound (A) of 1 or 2 carboxyl in expression aftermentioned 1 molecule.
As the diol compound (A) that has 1 or 2 carboxyl in 1 molecule that uses among the present invention, for example can enumerate the ester, 2 that the reaction by polyvalent alcohol and multi-anhydride obtains, 2-dihydroxymethyl lactic acid, 2,2-dimethylol propionic acid, 2,2-dimethylolpropionic acid, 2, dihydroxyl paraffinic acids such as 2-dihydroxymethyl valeric acid etc.As preferred compound, can enumerate 2,2-dimethylol propionic acid, 2, the 2-dimethylolpropionic acid.Wherein, dimethylol propionic acid or dimethylolpropionic acid obtain easily, are preferred.
As the diisocyanate cpd that uses among the present invention (B), can enumerate for example hexamethylene diisocyanate, 2,2, aliphatic diisocyanate compounds such as 4-trimethyl hexamethylene diisocyanate, isophorone diisocyanate, hydrogenation of benzene dimethyl vulcabond, 4, alicyclic diisocyanate compounds such as 4-cyclohexyl-methane vulcabond, the xylylene vulcabond, aromatic-aliphatic diisocyanate cpds such as tetramethyl-benzene dimethyl vulcabond, tolylene diisocyanate, aromatic diisocyanate compounds such as phenylmethane vulcabond.
Wherein, be difficult for taking place fast light variable color aspect from printed images and consider preferred aliphat diisocyanate cpd or alicyclic diisocyanate compound.
In above-mentioned general formula (1), R 1And R 3Preferably
(changing 4)
Figure BPA00001332752000061
The part-structure of expression.
In addition, in above-mentioned general formula (1), R 2Preferably
(changing 5)
The structure division of expression.
In the present invention, the index of Response of (formula 1) expression hydroxyl that refers to the isocyanide acyl group of diisocyanate cpd (B) and diol compound (A) resultant that reacts formation by 1: 1 molar ratio is 1 index.Namely, if during index of Response less than 0.95, unreacted diisocyanate cpd (B) and diol compound (A) are residual in a large number and since be in same system with subsequent handling in the diol compound that adds react, can not in urethane, import carboxyl equably.On the other hand, if index of Response surpasses 1.10, then isocyanide acyl group and carboxyl generation crosslinking reaction owing to form crosslinking structure, water-solublely descend significantly.
For above-mentioned diol compound (A) and above-mentioned diisocyanate cpd (B) are reacted, the resultant of reaction of the index of Response that obtains compound with above-mentioned general formula (1) expression and be principal constituent and (formula 1) expression in 0.95～1.10 scope (below, abbreviate resultant of reaction (1) as), for example, above-mentioned diol compound (A) and above-mentioned diisocyanate cpd (B) are added in the solvent that does not contain active hydrogen, make reaction soln remain 60～80 ℃ and react.Dialkyl ether, diester class, N-Methyl pyrrolidone, dimethyl formamide, ketone, diox, acetates, halogenated aromatic compounds etc. that diol compound is arranged as preferred solvent herein.
In reaction, the quantitative values of the hydroxyl value of monitoring reaction solution or isocyanide acyl group in the moment that reaches certain reactivity, namely is in moment termination reaction in 0.95～1.10 the scope at the index of Response of (formula 1) expression, obtains resultant of reaction (1) thus.As the method for termination reaction, owing to also need to make isocyanide acyl group and diol compound to react later on, preferably temperature of reaction is reduced to temperature that isocyanic ester reacts in fact hardly, as the method below 30 ℃.
The quantitative values of isocyanide acyl group herein can be obtained according to the method for record among the ISO14896 (test method of isocyanate group containing ratio), and the value that the quantitative values of the isocyanide acyl group of the quantitative values of the isocyanide acyl group that the reactivity of isocyanide acyl group can be by resultant of reaction before divided by reaction obtains is calculated.Specifically, obtain by following formula.
Isocyanide acyl group reactivity=1-(quantitative values of the isocyanide acyl group of resultant of reaction)/(quantitative values of the isocyanide acyl group before the reaction)
About the crosslinking reaction of above-mentioned isocyanide acyl group and carboxyl, also can change from the acid number of diisocyanate cpd (B) and diol compound (A) reaction front and back and infer.
As the mol ratio of above-mentioned diol compound (A) and above-mentioned diisocyanate cpd (B), specifically, preferably be in 1: 1.7～1: 2.2 the scope preferred especially 1: 2 at least.If mol ratio less than 1.7 then exists the content of compound of general formula (1) expression little, the monoisocyanates composition in the resultant of reaction (1) is many, and the carboxyl of urethane end imports ratio height, the situation of water-soluble reduction.In addition, if mol ratio surpasses 2.2, diisocyanate cpd (B) surplus then is easy to carry out the crosslinking reaction of isocyanide acyl group and carboxyl.
The content of the compound of contained above-mentioned general formula (1) expression is preferably more than 80% by the solids component ratio at least in the above-mentioned resultant of reaction (1), is preferably more than 90% especially.In the above-mentioned resultant of reaction (1) compound of contained above-mentioned general formula (1) expression contain quantity not sufficient 80% time, show that namely the monoisocyanates composition is many, exist the carboxyl of urethane end to import ratio height, the situation of water-soluble reduction.
For above-mentioned resultant of reaction (1), if long-time the placement then carried out the crosslinking reaction of isocyanide acyl group and carboxyl, form cross-linked polymer.Therefore preferably carry out subsequent processing rapidly, that is, make above-mentioned resultant of reaction (1) and diol compound (C), or above-mentioned resultant of reaction and diol compound (C) and diisocyanate cpd (D) react.
As with the diol compound (C) of above-mentioned resultant of reaction (1) reaction, so that in the macromolecular chain of urethane, evenly import the purpose of carboxyl, preferably do not contain carboxyl for designing.Other has no particular limits, and can suitably select according to the ink printing adaptability of expectation.For example, particularly under the situation of expectation erasibility, preferably give certain flexibility, preferred, polyethers polyvalent alcohol and polyester polyol to the waterborne polymeric that uses.In addition, because the amino-formate bond in the urethane that contains carboxyl that uses among the present invention has the tendency that the film hardness on the print that obtains is uprised, for the purpose that reduces the carbamate bond amount in 1 molecule, preferably use the diol compound of high molecular.But, if the too high molecule of molecular weight, then can influence printing ink discharge property, therefore the molecular weight of diol compound (C) is scaled after the number-average molecular weight preferred in 400～3000 scope, more preferably 500～2500 molecular weight (here, number-average molecular weight among the present invention is by gel permeation chromatography, and is expressed as the polystyrene conversion value.Unless below specialize, all abbreviate Mn as).
As the example of these diol compounds (C), can enumerate polyester polyol, polyether glycol, polyhydroxy polycarboxylic carbonic ether, polyhydroxy polycarboxylic acetal, polyhydroxy polycarboxylic acrylate, polyhydroxy polycarboxylic esteramides and polyhydroxy polycarboxylic thioether.Wherein preferred polyester polyvalent alcohol, polyether glycol and polyhydroxy polycarboxylic carbonic ether.These diol compounds can only make a kind of the reaction, also can mix multiple the reaction.
In addition, except above-mentioned high molecular diol compound, be purpose to regulate film hardness on the print etc., also can suitably and use low-molecular-weight diol compound.As an example, can enumerate ethylene glycol, Diethylene Glycol, propylene glycol, dipropylene glycol, 1,2-propylene glycol, 1, ammediol, 1,4-butyleneglycol etc.
In addition, as diisocyanate cpd (D), can suitably use the diisocyanate cpd that uses in the above-mentioned diisocyanate cpd (B).
In addition, in the present invention, can use chainextender as required, chainextender as this moment, for example can make spent glycol, propylene glycol, 1,4-butyleneglycol, 1,6-hexylene glycol 1,9-nonanediol, 1, two (beta-hydroxy oxyethyl group) benzene, 1 of 4-, glycolss such as 4-cyclohexanediol, xylylene glycol, quadrol, propylene diamine, xylylene diamines, isophorone diamine, 4,4 '-diaminodiphenylmethane, tolylene diamine, 4, in two amines such as 4 '-diamino-dicyclohexyl methane more than a kind or 2 kinds.
In order to make above-mentioned resultant of reaction (1) and diol compound (C), or above-mentioned resultant of reaction and diol compound (C) and diisocyanate cpd (D) reaction, react by known method and to get final product.
Make above-mentioned resultant of reaction (1) and diol compound (C) when reacting, can it be reacted by above-mentioned resultant of reaction (1) and diol compound (C) being mixed stir in solvent.
In addition, when making the reaction of above-mentioned resultant of reaction (1) and diol compound (C) and diisocyanate cpd (D), can mixing stirring in solvent it be reacted on one side above-mentioned resultant of reaction (1) and diol compound (C) one side, add diisocyanate cpd (D) then, also mixture and the above-mentioned resultant of reaction (1) of diol compound (C) and diisocyanate cpd (D) can be mixed stirring in solvent, it is reacted.In addition, according to purposes such as raising molecular weight, also can further add diol compound (C) again.
For concrete reaction, for example in the above-mentioned solvent that does not contain active hydrogen, under 60～110 ℃ condition, reacted 10～20 hours.At this moment, also can use known urethane catalyzer such as dibutyl tin laurate.Then, for the urethane that contains carboxyl that obtains and the mixture of organic solvent, make water and alkaline matter at leisure from oil phase to the water phase inversion, carry out desolventizing then, thereby can form the waterborne polymeric of the urethane that contains carboxyl.
The alkaline matter that uses during as phase inversion, for example can enumerate ammonia, ethamine, Trimethylamine 99, triethylamine, tri-isopropyl amine, Tributylamine, trolamine, N methyldiethanol amine, N-phenyldiethanol-amine, monoethanolamine, dimethylethanolamine, diethylethanolamine, morpholine, N-methylmorpholine, 2-amino-2-ethyl-organic amines such as 1-propyl alcohol, basic metal such as lithium, potassium, sodium, sodium hydroxide, these inorganic bases of potassium hydroxide etc.The usage quantity of alkaline matter can suitably be set according to the rerum natura of the urethane that contains carboxyl, but the usage quantity of alkaline matter has no particular limits, in using usually and the alkaline matter of 70～130% needed amounts of urethane acid number.
When the acid number of the urethane that contains carboxyl of Huo Deing was 20～70mgKOH/g like this, print qualities such as the discharge of the water-based ink for use in ink-jet recording of preparation has good stability, erasibility were also good, were preferred therefore.In addition, the above-mentioned quality molecular-weight average that contains the urethane of carboxyl is preferably 10,000～50,000, more preferably 20,000～50,000 (here, the quality molecular-weight average among the present invention is by gel permeation chromatography, and is expressed as the polystyrene conversion value.Unless below specialize, all abbreviate Mw as).If Mw less than 10,000, then possibility pigment is to the anchorage deficiency of printing medium, and the erasibility of printed images reduces simultaneously.On the other hand, if Mw surpasses 50,000, then the viscosity height of the water-based ink for use in ink-jet recording that may prepare is discharged stability and is reduced.
The waterborne polymeric by the polyurethane preparation that contains carboxyl that uses from the present invention has formed aqueous dispersion.The not enough 50nm of the particle diameter of preferred aqueous dispersion.If this particle diameter is more than the 50nm, then there is the dispersion stabilization deficiency of aqueous dispersion, the urethane that contains carboxyl when carrying out the printing ink discharge is for a long time separated out from printing ink, produces the situation of coking.
The mensuration of particle diameter can be implemented by known habitual centrifugal settling mode, laser diffraction mode (scattering of light mode), ESA mode, kapillary mode, electron microscope mode etc. herein.Preferably measure by the Microtrack UPA that utilizes dynamic light scattering method.
The above-mentioned urethane amount that contains carboxyl that cooperates in the dispersible pigment dispersion of the present invention cooperates ratio with pigment and difference is 20～200 mass parts with respect to pigment 100 mass parts preferably, more preferably 30～70 mass parts.When particularly using as water-based ink for use in ink-jet recording, if the use level of the above-mentioned urethane that contains carboxyl is few, then print quality such as erasibility reduces, if use level is excessive, then exists printing ink to discharge the situation that stability reduces.
(pigment)
For above-mentioned waterborne polymeric, demonstrating the good pigment-dispersing, the discharge stability that not influenced by pigment type also is its feature.As the pigment that is used for the configuration dispersible pigment dispersion, can enumerate mineral dyes such as barium sulfate, lead sulfate, titanium oxide, lead and yellow-collation, red iron oxide, chromic oxide, carbon black, anthraquione pigmentss ， perylene pigments, tetrazo (ジ ス ア ゾ) series pigments, phthualocyanine pigment, isoindoline series pigments ， dioxazine series pigments, quinoline a word used for translation ketone series pigments perylene ketone (ペ リ ノ Application) series pigments, benzimidazolone series pigments etc.These pigment can be used alone or as a mixture.
As black pigment, preferably use carbon blacks such as the furnace black of photostabilization excellence, strong covering power, dim, acetylene black, channel black, titanium black etc.
In addition, in the pigment dyestuff as the trichromatic indigo plant in the color (シ ア Application), fuchsin and Huang Wei representative, pigment illustration applicatory is as follows in the present invention.
As blue pigments, for example can enumerate C.I. pigment blue 1, C.I. Pigment blue 2, C.I. Pigment blue 3, C.I. pigment Blue 15, C.I. pigment Blue 15: 1, C.I. pigment Blue 15: 3, C.I. pigment Blue 15: 4, C.I. pigment blue 16, C.I. Pigment blue 22, C.I. pigment blue 60 etc.
As magenta pigments, for example can enumerate C.I. Pigment red 5, C.I. Pigment red 7, C.I. Pigment red 12, C.I. pigment red 48, C.I. pigment red 4 8:1, C.I. Pigment red 57, C.I. Pigment Red 112, C.I. pigment red 122, C.I. pigment red 123, C.I. pigment red 146, C.I. Pigment red 168, C.I. Pigment red 184, C.I. Pigment red 202, C.I. pigment violet 19 etc.
As yellow ultramarine, for example can enumerate C.I. Pigment Yellow 73 1, C.I. Pigment Yellow 73 2, C.I. Pigment Yellow 73 3, C.I. pigment Yellow 12, C.I. pigment yellow 13, C.I. pigment Yellow 14, C.I. Pigment Yellow 73 16, C.I. pigment yellow 17, C.I. Pigment Yellow 73 73, C.I. Pigment Yellow 73 74, C.I. Pigment Yellow 73 75, C.I. pigment yellow 83, C.I. Pigment Yellow 73 93, C.I. Pigment Yellow 73 95, C.I. Pigment Yellow 73 97, C.I. Pigment Yellow 73 98, C.I. Pigment Yellow 73 109, C.I. Pigment Yellow 73 114, C.I. pigment Yellow 12 8, C.I. pigment Yellow 12 9, C.I. pigment yellow 13 8, C.I. Pigment Yellow 73 151, C.I. pigment yellow 154, C.I. Pigment Yellow 73 155 etc.
For the particle diameter of above-mentioned pigment, preferred primary particle size is in the scope of 1～500nm, more preferably in the scope of 20～200nm.In addition, the pigment particle size after preferably disperseing in medium is in the scope of 10～300nm, more preferably in the scope of 50～150nm.The mensuration of pigment primary particle size can be implemented by electron microscope, gas or solute absorption method, airiness method, X ray small angle scattering method etc.The mensuration of the pigment particle size after the dispersion can be implemented by known habitual centrifugal settling mode, laser diffraction mode (scattering of light mode), ESA mode, kapillary mode, electron microscope mode etc.
(water)
As the water that uses among the present invention, except making water separately, also can be water and the mixed solvent formed by the water-miscible organic solvent of intermiscibility with water.As water-miscible organic solvent, for example can enumerate ketones such as acetone, methylethylketone, methyl butyl ketone, methyl iso-butyl ketone (MIBK); Alcohols such as methyl alcohol, ethanol, 2-propyl alcohol, 2-methyl isophthalic acid-propyl alcohol, 1-butanols, 2-methyl cellosolve; Tetrahydrofuran (THF), 1,4-diox, 1, ethers such as 2-glycol dimethyl ether; Amides such as dimethyl formamide, N-Methyl pyrrolidone preferably especially uses that to be selected from carbonatoms be that 3～6 ketone and carbonatoms are the compound of 1～5 alcohol.
(other composition colo(u)rant dispersion resin)
The urethane that contains carboxyl that uses among the present invention has the performance of dispersed color, therefore also can use as pigment-dispersing resin separately, also can and be used as the resin (being designated hereinafter simply as the colo(u)rant dispersion resin) that common pigment dispersing agent uses.Perhaps, also can be used to the purpose of vehicle.And the situation of usefulness under, the employed urethane that contains carboxyl and colo(u)rant dispersion have no particular limits in proper order with the interpolation of resin, can suitably change according to purpose.For example, the dispersible pigment dispersion of the present invention that obtains with the urethane dispersed color that contains carboxyl directly can be formed printing ink with solvent cut uses, also can be in the pigment dispersion that forms with resin dispersion with general colo(u)rant dispersion, the urethane that contains carboxyl that uses among follow-up interpolation the present invention forms dispersible pigment dispersion of the present invention.
As general colo(u)rant dispersion resin, the water-base resin that is suitable for the pigment preparation dispersion gets final product, as preferred example, for example can enumerate polyvinyl alcohol, Polyvinylpyrolidone (PVP), acrylic resins such as acrylic acid and acrylic ester copolymers, the styrene-propene acid copolymer, vinylbenzene-Sipacril 2739OF, vinylbenzene-methacrylic acid-acrylate copolymer, styrene--acrylic copolymer, styrene-propene acid resins such as styrene--acrylic acid and acrylic ester copolymers, styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, vinyl naphthalene-acrylic copolymer, and the salt of this water-base resin.
Compound as the salt that is used to form above-mentioned multipolymer, alkali hydroxide metal species such as sodium hydroxide, potassium hydroxide, lithium hydroxide be can enumerate, diethylamine, ammonia, ethamine, triethylamine, propylamine, Isopropylamine, dipropyl amine, butylamine, isobutylamine, trolamine, diethanolamine, amino methyl propyl alcohol, morpholine etc. reached.These usage quantitys that are used to form the compound of salt are preferably more than the neutralization equivalent of above-mentioned multipolymer.
These water-base resins can be used alone or in mixture of two or more in use.Also have, the water-base resin that herein uses is random copolymers, segmented copolymer etc., and its form has no particular limits.
Particularly under the situation of preparation water-based ink for use in ink-jet recording, in order to suppress the coking of heater section, obtain discharging the water color ink of excellent in stability, above-mentioned colo(u)rant dispersion preferably is in the Mw of resin in 6,000～20,000 the scope.If Mw is below 6,000, then the dispersion stabilization of water color ink itself may reduce, and on the other hand, if surpass 20,000, then has the viscosity height of water color ink, and the tendency of dispersion stabilization reduction.And serious for the coking of heater section, may become and cause the reason that can not discharge droplet of ink from the spray nozzle front end of hot ink jet type ink-jet printer.
It is 1～100 mass parts that above-mentioned colo(u)rant dispersion is preferably with respect to pigment 100 mass parts with the use level of resin, more preferably 2～70 mass parts.In addition, above-mentioned colo(u)rant dispersion is preferably 50～300mgKOH/g with the acid number of resin.
Particularly under the situation of preparation water-based ink for use in ink-jet recording, consider for preferred viewpoint from making dispersion stabilization etc., the preferred salt that uses vinylbenzene-(methyl) acrylic copolymer, if in the salt of using vinylbenzene-(methyl) acrylic copolymer in advance forms colo(u)rant dispersion in water aqueous liquid dispersion, add and above-mentionedly contain the urethane of carboxyl and prepare, then printing ink discharge property is excellent especially, and can obtain the printed images of erasibility excellence.
The method that obtains dispersible pigment dispersion of the present invention has no particular limits, and can be undertaken by known method.For example, can with the above-mentioned urethane that contains carboxyl with colo(u)rant dispersion in water or moisture aqueous solvent and the dispersible pigment dispersion of the present invention that forms directly with using as printing ink behind the solvent cut, also can be in the pigment dispersion that forms with resin dispersion with general colo(u)rant dispersion, the urethane that contains carboxyl that uses among follow-up interpolation the present invention, and form dispersible pigment dispersion of the present invention with solvent adjustment concentration as required.
Stirring, diverting device as being used for dispersed color for example can use known habitual various dispersion machines such as ultrasonic homogenizer, high-pressure homogenizer, paint mixer, ball mill, roller mill, sand mill (sand mill), sand milling (sand grinder), Dai Nuomo (Dyno-mill), Dispermat high speed dispersor, SC mill, Nanomizer.
(water-based ink for use in ink-jet recording)
Water-based ink for use in ink-jet recording of the present invention is to dilute dispersible pigment dispersion of the present invention with above-mentioned water or moisture aqueous solvent, and add dry inhibitor therein as required, penetrant or other additive be mixed with.
Dry inhibitor is the composition of giving the effect of the water-based ink for use in ink-jet recording drying in the ink jet jet hole that suppresses spray ink Printing brush head.Usually use the water-miscible organic solvent with the above boiling point of water boiling point.
As the water-miscible organic solvent that can be used as dry inhibitor, can enumerate polyalcohols such as ethylene glycol, Diethylene Glycol, polyoxyethylene glycol, glycerine, pyrrolidinone compounds such as N-N-methyl-2-2-pyrrolidone N-, 2-Pyrrolidone, amides, dimethyl formamide, imidazolone etc.As the usage quantity of dry inhibitor, when solvent is water, preferably use according to the scope that with respect to 100 parts in water is 1～150 part.
Penetrant is injected from the ink jet nozzle of ink jetting head in order to make, be attached to water-based ink for use in ink-jet recording on the recording medium soaks into to this recording medium easily and uses.By using penetrant, can make aqueous solvent to soaking into that recording medium is exceedingly fast, obtain image and ooze the record thing of spreading and sinking in few.
As the penetrant that uses among the present invention, can enumerate ethylene glycol, 1,2, polyalcohols such as 6-hexanetriol, thiodiglycol, hexylene glycol, Diethylene Glycol, glycols such as pentanediol, hexylene glycol, glycol ethers such as lauric acid propylene glycol ester, lower alcohols such as the low alkyl group ethers of polyvalent alcohols such as Diethylene Glycol ethyl ether, triethylene glycol list ethyl ether, ethanol, Virahol, Diethylene Glycol-glycol ethers such as N-butyl ether, water-miscible organic solvents such as propanediol derivative etc.These materials can separately or mix use more than 2 kinds.Use by mixing more than 2 kinds, can obtain preferred impregnability sometimes.
For water-based ink for use in ink-jet recording of the present invention, in order to regulate the rerum naturas such as surface tension of printing ink, also can add certain amount of surfactant.As tensio-active agent, have no particular limits, from anion surfactants such as alkylbenzene sulfonate, higher fatty acid salts, nonionogenic tensides such as polyethylene oxide alkyl ethers, polyethylene oxide fatty acid ester also have in the known habitual tensio-active agents such as cats product, amphoterics in addition and suitably select to get final product.These tensio-active agents can use separately, also can mix two or more uses in addition.
As other additive, for example can enumerate sanitas, mould inhibitor or prevent that nozzle bore from stopping up the intercalating agent of usefulness etc.
If there is oversize particle in the water-based ink for use in ink-jet recording, then can become the reason of the ink jet nozzle bore obstruction of ink-jet printer, therefore preferably after dispersion treatment, remove oversize particle by modes such as centrifugation or filtrations.
The printing ink excellent storage stability of the water-based ink for use in ink-jet recording of the present invention that obtains like this, discharge excellence from the ink jet nozzle of ink jetting head, use concentration, the glossiness height of the printing ink tunicle that this printing ink forms at recording medium, and the erasibility excellence.
Embodiment
Below, the present invention is described in detail by embodiment, but these embodiment are specifically described the present invention, and embodiment is not limited thereto.
In addition, in synthesis example, in embodiment and the comparative example, " part " reaches " % " and is the mass conversion value.
＜isocyanate group quantitatively
Test liquid 0.1g is joined among the dimethyl formamide solution 40ml of di-n-butyl amine of 0.01 equivalent and dissolves, then with tetrabromophenol sulfonphthalein as indicator, carry out neutralization titration with the methanol solution of the hydrochloric acid of 0.01 equivalent, thereby carry out quantitatively.
＜acid number quantitatively
With methylethylketone 10g dilution test liquid 1.0g, add toluene and methanol mixed solvent (toluene: dissolve among solution 40ml methyl alcohol=7: 3) to, then with phenolphthalein as indicator, carry out neutralization titration with the methanol solution of the potassium hydroxide of 0.1 equivalent, thereby carry out quantitatively.
(pigment particle size in the water-based ink for use in ink-jet recording is judged)
In ink samples, behind the thin up to 1000 times, use sreen analysis meter (Leeds ﹠amp; " the Microtrac UPA150 " that Northrup company makes), measure the particle diameter of the pigment that disperses in the sample printing ink.
＜synthesis example 1〉(synthesizing of resultant of reaction (1-1))
In the four-hole boiling flask with thermometer, agitator, nitrogen ingress pipe, cooling tube, add methylethylketone (being designated hereinafter simply as MEK) 482g, dimethylol propionic acid (being designated hereinafter simply as DMPA) 134g, tolylene diisocyanate 348g, nitrogen atmosphere, 70 ℃ of following reactions 1.5 hours, obtain resultant of reaction (1-1).The isocyanide acyl group quantitative values of resultant of reaction (1-1) is 8.73, and index of Response is 0.998.
＜synthesis example 2〉(synthesizing of resultant of reaction (1-2))
In the four-hole boiling flask with thermometer, agitator, nitrogen ingress pipe, cooling tube, add MEK660g, DMPA 134g, 4,4-cyclohexyl-methane vulcabond (being designated hereinafter simply as H2MDI) 524g nitrogen atmosphere, 70 ℃ of following reactions 1.5 hours, obtains resultant of reaction (1-2).The isocyanide acyl group quantitative values of resultant of reaction (1-2) is 6.53, and index of Response is 0.980.
＜synthesis example 3〉(synthesizing of resultant of reaction (1-3))
In the four-hole boiling flask with thermometer, agitator, nitrogen ingress pipe, cooling tube, add MEK592g, DMPA 147g, isophorone diisocyanate (being designated hereinafter simply as IPDI) 444g, nitrogen atmosphere, 70 ℃ of following reactions 2 hours, obtain resultant of reaction (1-3).The isocyanide acyl group quantitative values of resultant of reaction (1-3) is 6.53, and index of Response is 0.977.
＜synthesis example 4〉(synthesizing of resultant of reaction (1-4))
In the four-hole boiling flask with thermometer, agitator, nitrogen ingress pipe, cooling tube, add MEK592g, DMPA 147g, IPDI 444g, nitrogen atmosphere, 70 ℃ of following reactions 2.5 hours, obtain resultant of reaction (1-4).The isocyanide acyl group quantitative values of resultant of reaction (1-4) is 5.82, and index of Response is 1.068.
＜synthesis example 5〉(synthesizing of resultant of reaction (1-5))
In the four-hole boiling flask with thermometer, agitator, nitrogen ingress pipe, cooling tube, add MEK622g, DMPA 134g, IPDI 488g, nitrogen atmosphere, 70 ℃ of following reactions 2 hours, obtain resultant of reaction (1-5).The isocyanide acyl group quantitative values of resultant of reaction (1-5) is 8.17, and index of Response is 0.990.
＜synthesis example 1 relatively〉resultant of reaction (than 1-1) synthetic
In the four-hole boiling flask with thermometer, agitator, nitrogen ingress pipe, cooling tube, add MEK290g, DMPA 67g, IPDI 222g, nitrogen atmosphere, 70 ℃ of following reactions 1 hour, obtain resultant of reaction (than 1-1).The isocyanide acyl group quantitative values of resultant of reaction (than 1-1) is 4.49, and index of Response is 0.760.
＜synthesis example 2 relatively〉resultant of reaction (than 1-2) synthetic
In the four-hole boiling flask with thermometer, agitator, nitrogen ingress pipe, cooling tube, add MEK290g, DMPA 67g, IPDI 222g, nitrogen atmosphere, 70 ℃ of following reactions 6 hours, obtain resultant of reaction (than 1-2).The isocyanide acyl group quantitative values of resultant of reaction (than 1-2) is 3.11, and index of Response is 1.140.
The physics value of above-mentioned resultant of reaction (1-1)～(1-5) and (than 1-1)～(than 1-2) is shown in Table 1.
[table 1]
Figure BPA00001332752000161
※ represents the mole number of mole number/diol compound (A) of diisocyanate cpd (B)
＜synthesis example 6〉(urethane A synthetic that contains carboxyl)
In the four-hole boiling flask with thermometer, agitator, nitrogen ingress pipe, cooling tube, the resultant of reaction that adding is obtained by synthesis example 1 (1-1) 243g and Mn are 650 poly-(oxygen tetramethylene) glycol (OH base equivalent 173) 243g, dibutyl tin laurate (being designated hereinafter simply as DBTDL) 0.001g, MEK 243g, in nitrogen atmosphere, 80 ℃ reaction after 16 hours down, add methyl alcohol 5g termination reaction, obtain acid number 38, polystyrene conversion quality molecular-weight average and be the MEK solution of 12,000 the urethane A that contains carboxyl.For the solution that obtains, use with the DMPA that adds with the neutralization of the sodium hydroxide of molar weight, add water and carry out Phase inversion emulsification, remove MEK by the decompression desolventizing after, adding water, to form the mass conversion solids component be 20% the aqueous solution.The aqueous solution is water white, the not enough 50nm of particle diameter.
＜synthesis example 7〉(urethane B synthetic that contains carboxyl)
In the four-hole boiling flask with thermometer, agitator, nitrogen ingress pipe, cooling tube, the resultant of reaction that adding is obtained by synthesis example 2 (1-2) 333g and Mn are 1000 poly-(oxygen tetramethylene) glycol (OH base equivalent 112) 260g, DBTDL 0.001g, MEK 260g, in nitrogen atmosphere, 80 ℃ reaction after 16 hours down, add methyl alcohol 5g termination reaction, obtain acid number 33, Mw and be 50,000 the urethane B that contains carboxyl.For the resin solution that obtains, use with the DMPA that adds with the neutralization of the sodium hydroxide of molar weight, add water and carry out Phase inversion emulsification, remove MEK by the decompression desolventizing after, adding water, to form the mass conversion solids component be 20% the aqueous solution.The aqueous solution is water white, the not enough 50nm of particle diameter.
＜synthesis example 8〉(urethane C synthetic that contains carboxyl)
In the four-hole boiling flask with thermometer, agitator, nitrogen ingress pipe, cooling tube, the resultant of reaction that adding is obtained by synthesis example 3 (1-3) 296g and Mn are 1000 poly-(oxygen tetramethylene) glycol (OH base equivalent 112) 225g, DBTDL 0.001g, MEK 230g, in nitrogen atmosphere, 80 ℃ reaction after 16 hours down, add methyl alcohol 5g termination reaction, obtain acid number 41, Mw and be 30,000 the urethane C that contains carboxyl.For the resin solution that obtains, use with the DMPA that adds with the neutralization of the sodium hydroxide of molar weight, add water and carry out Phase inversion emulsification, remove MEK by the decompression desolventizing after, adding water, to form the mass conversion solids component be 20% the aqueous solution.The aqueous solution is water white, the not enough 50nm of particle diameter.
＜synthesis example 9〉(urethane D synthetic that contains carboxyl)
In the four-hole boiling flask with thermometer, agitator, nitrogen ingress pipe, cooling tube, the resultant of reaction that adding is obtained by synthesis example 4 (1-4) 296g and Mn are 1000 poly-(oxygen tetramethylene) glycol (OH base equivalent 112) 225g, DBTDL 0.001g, MEK 230g, in nitrogen atmosphere, 80 ℃ reaction after 16 hours down, add methyl alcohol 5g termination reaction, obtain acid number 41, Mw and be 30,000 the urethane D that contains carboxyl.For the resin solution that obtains, use with the DMPA that adds with the neutralization of the sodium hydroxide of molar weight, add water and carry out Phase inversion emulsification, remove MEK by the decompression desolventizing after, adding water, to form the mass conversion solids component be 20% the aqueous solution.The aqueous solution is water white, the not enough 50nm of particle diameter
＜synthesis example 10〉(urethane E synthetic that contains carboxyl)
In the four-hole boiling flask with thermometer, agitator, nitrogen ingress pipe, cooling tube, the resultant of reaction that adding is obtained by synthesis example 2 (1-2) 330g and Mn are 650 polyester polyol (OH base equivalent 173) 169g, DBTDL 0.001g, MEK 170g, in nitrogen atmosphere, 80 ℃ reaction after 20 hours down, add methyl alcohol 5g termination reaction, obtain acid number 42, Mw and be 60,000 the urethane E that contains carboxyl.For the resin solution that obtains, use with the DMPA that adds with the neutralization of the sodium hydroxide of molar weight, add water and carry out Phase inversion emulsification, remove MEK by the decompression desolventizing after, adding water, to form the mass conversion solids component be 20% the aqueous solution.The aqueous solution is water white, the not enough 50nm of particle diameter
＜synthesis example 11〉(urethane F synthetic that contains carboxyl)
In the four-hole boiling flask with thermometer, agitator, nitrogen ingress pipe, cooling tube, the resultant of reaction that adding is obtained by synthesis example 1 (1-1) 243g and Mn are 650 poly-(oxygen tetramethylene) glycol (OH base equivalent 173) 270g, DBTDL 0.001g, MEK 270g, in nitrogen atmosphere, 80 ℃ reaction after 10 hours down, add methyl alcohol 5g termination reaction, obtain acid number 36, Mw and be 9,000 the urethane F that contains carboxyl.For the resin solution that obtains, use with the DMPA that adds with the neutralization of the sodium hydroxide of molar weight, add water and carry out Phase inversion emulsification, remove MEK by the decompression desolventizing after, adding water, to form the mass conversion solids component be 20% the aqueous solution.The aqueous solution is water white, the not enough 50nm of particle diameter
＜synthesis example 12〉(urethane G synthetic that contains carboxyl)
In the four-hole boiling flask with thermometer, agitator, nitrogen ingress pipe, cooling tube, the resultant of reaction that adding is obtained by synthesis example 1 (1-1) 243g and Mn are 2000 poly-(oxygen tetramethylene) glycol (OH base equivalent 56) 667g, IPDI 12.3g, DBTDL 0.001g, MEK 680g, in nitrogen atmosphere, 80 ℃ reaction after 16 hours down, add methyl alcohol 5g termination reaction, obtain acid number 17, Mw and be 38,000 the urethane G that contains carboxyl.For the resin solution that obtains, use with the DMPA that adds with the neutralization of the sodium hydroxide of molar weight, add water and carry out Phase inversion emulsification, remove MEK by the decompression desolventizing after, adding water, to form the mass conversion solids component be 20% the aqueous solution.The aqueous solution is the fluorescence color clear solution, and particle diameter is 80nm.
＜synthesis example 13〉(urethane H synthetic that contains carboxyl)
In the four-hole boiling flask with thermometer, agitator, nitrogen ingress pipe, cooling tube, the resultant of reaction that adding is obtained by synthesis example 3 (1-3) 268g and Mn are 400 polypropylene glycol (OH base equivalent 281) 45g, ethylene glycol 7.2g, DBTDL 0.001g, MEK 320g, in nitrogen atmosphere, 80 ℃ reaction after 16 hours down, add methyl alcohol 5g termination reaction, obtain acid number 75, Mw and be 30,000 the urethane H that contains carboxyl.For the resin solution that obtains, use with the DMPA that adds with the neutralization of the sodium hydroxide of molar weight, add water and carry out Phase inversion emulsification, remove MEK by the decompression desolventizing after, adding water, to form the mass conversion solids component be 20% the aqueous solution.The aqueous solution is water white, the not enough 50nm of particle diameter.
＜synthesis example 14〉(urethane I synthetic that contains carboxyl)
In the four-hole boiling flask with thermometer, agitator, nitrogen ingress pipe, cooling tube, the resultant of reaction that adding is obtained by synthesis example 5 (1-5) 293g and Mn are 2000 poly-(oxygen tetramethylene) glycol (OH base equivalent 56) 450g, DBTDL 0.001g, MEK 450g, in nitrogen atmosphere, 80 ℃ reaction after 16 hours down, add methyl alcohol 5g termination reaction, obtain acid number 28, Mw and be 40,000 the urethane I that contains carboxyl.For the resin solution that obtains, use with the DMPA that adds with the neutralization of the sodium hydroxide of molar weight, add water and carry out Phase inversion emulsification, remove MEK by the decompression desolventizing after, adding water, to form the mass conversion solids component be 20% the aqueous solution.The aqueous solution is water white, the not enough 50nm of particle diameter.
＜synthesis example 3 relatively〉(urethane H-J synthetic that contains carboxyl)
In the four-hole boiling flask with thermometer, agitator, nitrogen ingress pipe, cooling tube, adding IPDI266g, DMPA 67g and Mn are 650 polyester polyol (OH base equivalent 173) 325g, DBTDL0.001g, MEK 646g, in nitrogen atmosphere, 80 ℃ reaction after 10 hours down, adding is as the quadrol 15g termination reaction of chainextender, obtain acid number 45, Mw and be 80,000 the urethane H-J that contains carboxyl.For the resin solution that obtains, use with the DMPA that adds with the neutralization of the sodium hydroxide of molar weight, add water and carry out Phase inversion emulsification, remove MEK by the decompression desolventizing after, adding water, to form the mass conversion solids component be 20% the aqueous solution.The aqueous solution is oyster white, and particle diameter is 200nm.
＜synthesis example 4 relatively〉(urethane H-K synthetic that contains carboxyl)
In the four-hole boiling flask with thermometer, agitator, nitrogen ingress pipe, cooling tube, add IPDI105g, DMPA 67g and MEK 172g,, nitrogen atmosphere, 70 ℃ of following reactions 4 hours, obtain oligourethane I1.In four-hole boiling flask, add IPDI 117g, Mn and be 650 poly-(oxygen tetramethylene) glycol (OH base equivalent 173) 357g, DBTDL 0.001g, MEK 474g, in nitrogen atmosphere, 80 ℃ reaction 6 hours down, obtain oligourethane I2.Add oligourethane I1344g in the solution 948g of described oligourethane I2, nitrogen atmosphere, 80 ℃ down reaction add methyl alcohol 5g termination reaction after 10 hours, obtain acid number 45, Mw and be 12,000 the urethane H-K that contains carboxyl.For the resin solution that obtains, use with the DMPA that adds with the neutralization of the sodium hydroxide of molar weight, add water and carry out Phase inversion emulsification, remove MEK by the decompression desolventizing after, adding water, to form the mass conversion solids component be 20% the aqueous solution.The aqueous solution is oyster white, and particle diameter is 100nm.
＜synthesis example 5 relatively〉(urethane H-L synthetic that contains carboxyl)
In the four-hole boiling flask with thermometer, agitator, nitrogen ingress pipe, cooling tube, add IPDI222g, Mn and be 650 poly-(oxygen tetramethylene) glycol (OH base equivalent 173) 330g, DBTDL0.001g, in nitrogen atmosphere, 100 ℃ reaction 2 hours down.Then, add DMPA 67g and MEK 620g, nitrogen atmosphere, 80 ℃ down reaction add methyl alcohol 5g termination reaction after 16 hours, obtain acid number 45, Mw and be 50,000 the urethane H-L that contains carboxyl.For the resin solution that obtains, use with the DMPA that adds with the neutralization of the sodium hydroxide of molar weight, add water and carry out Phase inversion emulsification, remove MEK by the decompression desolventizing after, adding water, to form the mass conversion solids component be 20% the aqueous solution.The aqueous solution is oyster white, and particle diameter is 150nm.
＜synthesis example 6 relatively〉(urethane H-M synthetic that contains carboxyl)
In the four-hole boiling flask with thermometer, agitator, nitrogen ingress pipe, cooling tube, resultant of reaction (than 1-1) 579g, the Mn that adding is obtained by comparison synthesis example 1 is 650 poly-(oxygen tetramethylene) glycol (OH base equivalent 173) 357g, DBTDL 0.001g, MEK 357g, in nitrogen atmosphere, 80 ℃ reaction after 16 hours down, add methyl alcohol 5g termination reaction, obtain acid number 45, Mw and be 32,000 the urethane H-M that contains carboxyl.For the resin solution that obtains, use with the DMPA that adds with the neutralization of the sodium hydroxide of molar weight, add water and carry out Phase inversion emulsification, remove MEK by the decompression desolventizing after, adding water, to form the mass conversion solids component be 20% the aqueous solution.The aqueous solution is oyster white, and particle diameter is 150nm.
＜synthesis example 7 relatively〉(urethane H-N synthetic that contains carboxyl)
In the four-hole boiling flask with thermometer, agitator, nitrogen ingress pipe, cooling tube, resultant of reaction (than 1-2) 579g, the Mn that adding is obtained by comparison synthesis example 2 is 650 poly-(oxygen tetramethylene) glycol (OH base equivalent 173) 357g, DBTDL 0.001g, MEK 357g, in nitrogen atmosphere, 80 ℃ reaction after 16 hours down, add methyl alcohol 5g termination reaction, obtain acid number 41, Mw and be 42,000 the urethane H-N that contains carboxyl.For the resin solution that obtains, use with the DMPA that adds with the neutralization of the sodium hydroxide of molar weight, add water and carry out Phase inversion emulsification, remove MEK by the decompression desolventizing after, adding water, to form the mass conversion solids component be 20% the aqueous solution.The aqueous solution is oyster white, and particle diameter is 200nm.
＜embodiment 1 〉
(preparation of aqueous pigment dispersions (a))
The solids component that adds benzyl methacrylate-Sipacril 2739OF in 250mL polyethylene bottle (Port リ PVC Application) is 50% methyl ethyl ketone solution (acid number 100, quality molecular-weight average 20,000) 6 part, 6.0 parts of 5% potassium hydroxide aqueous solutions, 10 parts of phthualocyanine pigments " Fastogen (registered trademark) Blue TGR " (DIC (strain) society system), 23.8 parts in water also mixes that (for each addition herein, the copper phthalocyanine series pigments is 10 parts, resin is for counting the amount of 30 quality % ratios by nonvolatile component with respect to pigment, 5% potassium hydroxide aqueous solution is with in the acid number of resin and 100% amount, water is that to make the nonvolatile component of mixed solution be 30% needed amount).
With paint regulator (using the zirconium oxide bead of diameter 0.5mm) this mixed solution was disperseed 2 hours.After disperseing to finish, for removing the liquid that obtains behind the zirconium oxide bead, heat up in a steamer methylethylketone with vaporizer, carry out centrifugation then and handle (8200G, 30 minutes), remove oversize particle, add pure water afterwards and regulate nonvolatile component, obtain nonvolatile component and be 20% aqueous pigment dispersions (a).The particle diameter of the pigment dispersion that obtains is 110nm.
The aqueous solution of the urethane A that contains carboxyl that uses this aqueous pigment dispersions (a) and obtained by synthesis example 6, prepare by following composition, and filter with the strainer of aperture 6 μ m, be mixed with pigment concentration and be 4% hot ink jet type water-based ink for use in ink-jet recording (a-A).
Figure DEST_PATH_GPA00001332751500021
＜embodiment 2～9 〉
Use aqueous solution B～I of the urethane that contains carboxyl that is obtained by synthesis example 7～14 of equivalent to replace the water solution A of the urethane that contains carboxyl that cooperates among the embodiment 1, in addition, carry out 1 identical operations with embodiment, be mixed with water-based ink for use in ink-jet recording (a-B)～(a-I).
＜embodiment 10 〉
(preparation of aqueous pigment dispersions (b))
The solids component that adds benzyl methacrylate-Sipacril 2739OF in the 250mL polyethylene bottle is 50% methyl ethyl ketone solution (acid number 100, quality molecular-weight average 20,000) 10 part, 10.0 parts of 5% potassium hydroxide aqueous solutions, 10 parts of quinoline a word used for translation ketone series pigments " Fastogen (registered trademark) Super Magenta RG " (DIC (strain) society system), 20.0 parts in water also mixes that (for each addition herein, quinoline a word used for translation ketone series pigments is 10 parts, resin is for counting the amount of 50 quality % ratios by nonvolatile component with respect to pigment, 5% potassium hydroxide aqueous solution is with in the acid number of resin and 100% amount, water is that to make the nonvolatile component of mixed solution be 30% needed amount).
With paint regulator (using the zirconium oxide bead of diameter 0.5mm) this mixed solution was disperseed 2 hours.After disperseing to finish, for removing the liquid that obtains behind the zirconium oxide bead, heat up in a steamer methylethylketone with vaporizer, carry out centrifugation then and handle (8200G, 30 minutes), remove oversize particle, add pure water afterwards and regulate not
The aqueous solution of the urethane A that contains carboxyl that uses this aqueous pigment dispersions (b) and obtained by synthesis example 6, prepare by following composition, and filter with the strainer of aperture 6 μ m, be mixed with pigment concentration and be 6% hot ink jet type water-based ink for use in ink-jet recording (b-A).
＜embodiment 11～12 〉
Use aqueous solution B～C of the urethane that contains carboxyl that is obtained by synthesis example 7～8 of equivalent to replace the water solution A of the urethane that contains carboxyl that cooperates among the embodiment 10, in addition, carry out 10 identical operations with embodiment, be mixed with water-based ink for use in ink-jet recording (b-B)～(b-C).
＜embodiment 13 〉
(preparation of aqueous pigment dispersions (c))
In the 250mL polyethylene bottle, add 10 parts of MEK solution, 4.0 parts of 5% potassium hydroxide aqueous solutions, 10 parts of phthualocyanine pigments " Fastogen (registered trademark) Blue TGR " (DIC (strain) society system), 26.8 parts in the water of the urethane A contain carboxyl and mix (for each addition herein, the copper phthalocyanine series pigments be 10 parts, resin for the amount, 5% potassium hydroxide aqueous solution of with respect to pigment, counting 50 quality % ratios by nonvolatile component for in the acid number of resin and 100% amount, water be that to make the nonvolatile component of mixed solution be 30% needed amount).
With paint regulator (using the zirconium oxide bead of diameter 0.5mm) this mixed solution was disperseed 2 hours.After disperseing to finish, for removing the liquid that obtains behind the zirconium oxide bead, heat up in a steamer methylethylketone with vaporizer, carry out centrifugation then and handle (8200G, 30 minutes), remove oversize particle, add pure water afterwards and regulate nonvolatile component, obtain nonvolatile component and be 20% aqueous pigment dispersions (c).The particle diameter of the pigment dispersion that obtains is 110nm.
Use this aqueous pigment dispersions (c), prepare by following composition, and filter with the strainer of aperture 6 μ m, be mixed with hot ink jet type water-based ink for use in ink-jet recording (c).
＜embodiment 14 〉
Use the MEK solution of the urethane C that contains carboxyl that is obtained by synthesis example 8 of equivalent to replace the MEK solution of the urethane A that contains carboxyl that obtained by synthesis example 6, in addition, carry out 13 identical operations with embodiment, obtain aqueous pigment dispersions d.The particle diameter of the pigment dispersion that obtains is 120nm.Use this aqueous pigment dispersions d, carry out the cooperation identical with embodiment 13, be mixed with water-based ink for use in ink-jet recording (d).
＜comparative example 1～5 〉
Use the water solution A by the urethane of allocating among the aqueous polyurethane H-J that contains carboxyl～H-N replacement embodiment 1 that relatively synthesis example 3～7 obtains that contains carboxyl of equivalent, in addition, carry out 1 identical operations with embodiment, be mixed with water-based ink for use in ink-jet recording (a-H-J)～(a-H-N).
＜performance test and judgement criteria 〉
(ink-vapor recording test (printing concentration, gloss number))
Bubble Jet (registered trademark) record-header (BC-30E has been loaded in use, Canon Co., Ltd's system) hot ink jet type ink-jet printer BJ F300 type (Canon Co., Ltd's system, hereinafter referred to as the machine of evaluation A), perhaps hot ink jet type ink-jet printer DJ 970CX i type (Co., Ltd. of Japanese Hewlett-Packard system, hereinafter referred to as the machine of evaluation B), describe at recording medium with ink samples, discharge stability test, the test of printing concentration, gloss number test and scuff test.
As recording medium, " Canon PB paper " or " Xerox4024 " of Xerox company manufacturing that common paper uses Canon (strain) to make are as " the description paper gloss " of ink-jet dedicated paper use Seiko Epson (strain) manufacturing.
(discharging stability)
The continuous full width of cloth image (ベ タ portrait) of printing on common paper, it is stable just more good that the printing number of print that is judged to be continuous printing more many (can not produce on image not discharges waits entanglement and the number that prints) is discharged, and judges by following 3 grade standards.
The printing number of zero print is more than 300
The printing number of △ print is more than 100 and is less than 300
The printing number of * print is for being less than 100
(printing concentration)
At the full width of cloth image of ink-jet dedicated paper printing, use printing concentration determination machine " GRETAG (registered trademark) D196, Gretag Macbeth corporate system ", measure the rendered image concentration of 5 points on the individual sample, with their mean value as printing concentration.Numerical value is more big to show that printing concentration is more good, judges by following 3 grade standards.
Zero lettering concentration is more than 2.5.
△ lettering concentration is more than 2.0 and less than 2.5.
* lettering concentration is less than 2.0.
(gloss number of image is measured)
At the full width of cloth image of dedicated paper printing, use " Haze-Gloss Meter, BYK Gardner corporate system " to measure machine as gloss number, under the mensuration angle of 20 degree, measure the gloss of rendered image.Measure 3 points on the single sample, with their mean value as gloss number.The more big expression gloss of numerical value is more good, judges by following 4 grade standards.
The ◎ gloss number is more than 40
Zero gloss number is more than 30.
The △ gloss number is more than 20 and less than 30.
* gloss number is less than 10.
(erasibility)
At the full width of cloth image of ink-jet dedicated paper printing, use and learn vibration shape rub resistance trier, make packing paper (as て Paper) with common paper, friction is 5 times under 200g load.The gloss number of print before and after the determination test, the more few erasibility that shows of the velocity of variation of gloss number is more good, judges by following 4 grade standards.
◎ gloss velocity of variation is less than 5%.
Zero gloss velocity of variation is more than 5% and less than 10%.
△ gloss velocity of variation is more than 10% and less than 15%.
* gloss velocity of variation is more than 15%.
(storage stability of ink for ink-jet recording)
Measuring ink for ink-jet recording 70 ℃ of viscosity after preserving 7 days down, is zero with the velocity of variation with respect to initial viscosity less than 5%, with more than 5% and less than 10% being △, with more than 10% be *.Here, use RE-550 type viscometer (eastern machine industry society system) to carry out viscosimetric analysis.
The performance test result of aqueous pigment dispersions of the present invention and water-based ink for use in ink-jet recording is shown in the table with gathering.
[table 2]
Figure BPA00001332752000251
By result shown in the table 2 as can be known, use the water-based ink for use in ink-jet recording that the urethane that contains carboxyl of the present invention forms storage stability, discharge excellent in stability, the ink jet printing thing gloss that obtains is more excellent, have high rendered image concentration, have high anti-brush.Particularly contain the molecular weight of urethane of carboxyl in 10000 to 50000 scope, and the embodiment 1～4 of acid number in 20 to 70 scope, 9～12 discharge stability be more than 300, gloss number has demonstrated very excellent value more than 40.
For embodiment 5, because molecular weight is 60000 such height, though therefore erasibility excellence, discharge property is poor slightly.In addition, for embodiment 6, because molecular weight is 8000 so low, though therefore discharge property is good, erasibility is poor slightly.For embodiment 7, because acid number is low, so particle diameter is big slightly, is 80nm, and discharge property is poor slightly.In addition, for embodiment 8, because the acid number height, erasibility is poor slightly.
Relative therewith, comparative example 1, comparative example 2, comparative example 3 are the example that does not contain resultant of reaction (1) in the urethane that contains carboxyl, and its discharge stability and erasibility are all low.Comparative example 4 is the low examples of index of Response, and comparative example 5 is the high examples of index of Response in addition, and it discharges stable non-constant.

Claims (3)

1. the manufacture method of a waterborne polymeric, it is at Yi Shui, waterborne polymeric and pigment are as the manufacture method of the waterborne polymeric that uses in must the dispersible pigment dispersion of composition, it is characterized in that, the diol compound (A) and the diisocyanate cpd (B) that have 1 or 2 carboxyl in 1 molecule are reacted, making the index of Response of calculating by (formula 1) is in 0.95～1.10 scope, with the compound of general formula (1) the expression resultant of reaction as principal constituent, then, make above-mentioned resultant of reaction and diol compound (C), above-mentioned resultant of reaction and diol compound (C) and diisocyanate cpd (D) are reacted;
Figure FPA00001332751400011
In the general formula (1), R 1And R 3The structure of the part of removing the isocyanide acyl group of expression diisocyanate cpd (B), R 1And R 3Can be identical, also can be different, R 2Represent to have in above-mentioned 1 molecule structure of the part of removing hydroxyl of the diol compound (A) of 1 or 2 carboxyl;
Index of Response=(reactivity of isocyanide acyl group) * (mole number of the mole number/diol compound (A) of diisocyanate cpd (B))
(formula 1).
2. the manufacture method of the described waterborne polymeric of claim 1, the acid number of described waterborne polymeric is 20～70mgKOH/g.
3. the manufacture method of claim 1 or 2 described waterborne polymerics is used for the dispersible pigment dispersion that water-based ink for use in ink-jet recording is used.
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Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8563634B2 (en) 2009-02-03 2013-10-22 Hewlett-Packard Development Company, L.P. Inkjet ink including polyurethane
EP2393888B1 (en) * 2009-02-03 2015-06-03 Hewlett-Packard Development Company, L.P. An inkjet ink including polyurethane
JP5950512B2 (en) * 2010-08-31 2016-07-13 キヤノン株式会社 Ink, ink cartridge, and ink jet recording method
JP5882628B2 (en) * 2010-08-31 2016-03-09 キヤノン株式会社 Ink, ink cartridge, and ink jet recording method
JP5413702B2 (en) * 2011-09-09 2014-02-12 Ｄｉｃ株式会社 Composite pigment and method for producing the same
JP5878722B2 (en) * 2011-09-30 2016-03-08 大日本塗料株式会社 Water-based pigment ink composition and printing method thereof
CN102746714A (en) * 2012-05-02 2012-10-24 中国皮革和制鞋工业研究院 Preparation method for transference resistance leather dye
JP2015120818A (en) * 2013-12-24 2015-07-02 Dic株式会社 Aqueous pigment dispersion and inkjet recording aqueous ink
CN106232743B (en) * 2014-04-18 2019-08-27 蓝宝迪有限公司 Additive for jetted ink
JP6398732B2 (en) * 2015-01-13 2018-10-03 Dic株式会社 Aqueous pigment dispersion and water-based ink for inkjet recording
WO2016175871A1 (en) 2015-04-27 2016-11-03 Hewlett-Packard Development Company, L.P. White inks
WO2016175738A1 (en) 2015-04-27 2016-11-03 Hewlett-Packard Development Company, L.P. White inks
US10273374B2 (en) 2015-04-27 2019-04-30 Hewlett-Packard Development Company, L.P. Fluid sets for inkjet imaging
WO2016175743A1 (en) 2015-04-27 2016-11-03 Hewlett-Packard Development Company, L.P. Fluid sets for inkjet imaging
BR112017018633B1 (en) 2015-04-27 2022-04-19 Hewlett-Packard Development Company, L.P. white paints
US10167406B2 (en) 2015-04-27 2019-01-01 Hewlett-Packard Development Company, L.P. White pigment dispersions
EP3647382B1 (en) * 2017-06-27 2023-09-06 FUJIFILM Corporation Inkjet ink for textile printing, ink cartridge, ink set, and inkjet textile printing method
JP2019023266A (en) * 2017-07-25 2019-02-14 三洋化成工業株式会社 Composite particle aqueous dispersion
EP3694899B1 (en) * 2017-10-11 2023-08-23 Eastman Kodak Company Compositions d'encres aqueuses pour impressions par jet d'encre et ensembles d'encre
WO2020102788A1 (en) 2018-11-17 2020-05-22 International Imaging Materials, Inc. Outdoor durable inkjet inks
EP3933001A4 (en) * 2019-02-28 2022-04-20 FUJIFILM Corporation Colored resin particle dispersion, ink, ink set, and inkjet printing method
CN109880038B (en) * 2019-03-05 2021-09-28 广州浦利姆环保科技有限公司 Waterborne polyurethane, preparation method thereof and waterborne color paste
MX2022000566A (en) 2019-07-16 2022-02-10 Basf Coatings Gmbh One-pack polyurethane dispersions, their manufacture and use.
EP4323423A1 (en) 2021-04-16 2024-02-21 Basf Se Aqueous polyurethane and polyurethane/poly(meth)acrylate hybrid dispersions

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3264723B2 (en) 1993-03-26 2002-03-11 キヤノン株式会社 Inkjet recording liquid, inkjet recording method using the same, recording unit, ink cartridge, and inkjet recording apparatus
DE69420065T2 (en) * 1993-03-15 2000-04-20 Canon Kk Ink, ink jet recording method using the same, and apparatus
JPH08218015A (en) * 1995-02-14 1996-08-27 Dainippon Ink & Chem Inc Polymer fine particle for jet ink and jet ink containing the same
JP4867085B2 (en) 2000-06-14 2012-02-01 三菱化学株式会社 Recording liquid and ink jet recording method
DE60107764T2 (en) * 2000-06-14 2006-03-02 Mitsubishi Chemical Corp. Recording liquid and ink jet recording method
US7176248B2 (en) * 2002-01-16 2007-02-13 E. I. Du Pont De Nemours And Company Smear resistant inkjet inks
JP4174666B2 (en) 2003-04-01 2008-11-05 セイコーエプソン株式会社 Ink composition for ink jet recording and recording method using the ink composition
JP3922460B2 (en) * 2004-01-23 2007-05-30 大日本インキ化学工業株式会社 Polymer fine particles for jet ink and jet ink
DE102005005846A1 (en) * 2005-02-08 2006-08-17 Basf Ag Solid pigment preparations containing water-soluble polyurethane-based surface-active additives
JP2008024733A (en) * 2006-07-18 2008-02-07 Toray Ind Inc Aqueous pigment dispersion and ink composition comprised of the same

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US8198391B2 (en) 2012-06-12
CN102165024A (en) 2011-08-24
CA2738462C (en) 2013-07-02
KR20110031225A (en) 2011-03-24
JPWO2010035665A1 (en) 2012-02-23
EP2341110B1 (en) 2018-05-16
HK1157373A1 (en) 2012-06-29
WO2010035665A1 (en) 2010-04-01
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EP2341110A1 (en) 2011-07-06
TW201016802A (en) 2010-05-01

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